Polyazo dyes derived from tetrazotized halogenated 4.4&#39;-diaminodiphenyl-methanes



Patented Jan. 1, 1929.

UNITED STATES PATENT OFFICE.

RUDOLPH KRECH, OF BERLIN-TREPTOW, AND ERICH KEINER, 0F BERLIN-WILMERSDORF, GERMANY, ASSIGNORS, BY MESNE ASSIGNMENTS, TO GRASSELLICORPORATION, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE.

nYEsrUrE POLYAZO DYES DERIVED FROM TE'IRAZOTIZED HALOGENATED 4.4-D'IAMINO DIPHENYL-METHAN ES.

No Drawing. Application filed December 4, 1925, Serial .N' 0. 73,254,and in Germany December 16, 1924.

By the present invention dyestuffs of outstanding properties offastness, and in particular of very good fastness to fulling and light,are obtained by coupling with azo components the4-diaz0-4-diazo-compound of chloro-substituted4.4'-diaminodiphenylmethane or a homologue thereof; for instance 4.4-diamino-3.3 -dichlorodiphenylmethane, 4.4 diamino 3.3 dimethyl 2.2-dichlorodiphenylmethane, 4.4 diamino-3.3.6.6-tetrachlorodiphenylmethane.

These parent materials can. be obtained by condensation of thecorresponding chloroanilines with formaldehyde and conversion of thecondensation product.

The following examples illustrate the invention. without limiting it,the parts being by'weight: o

1. 34 parts of 4.4'-diamino-3.3-dichlorodiphenylmethane dihydrochlorideare suspended in 150 parts of crude hydrochloric acid of 32 per centstrength and 250 parts of water, and then diazotized as usual at 0 C.The diazo-solution is then combined with 52 parts of sodiumQ-naphthol-4-sulphonate in solution alkaline with sodium carbonate. Themixture is heated on the water bath to about 75 C. and the dyestuff issalted out.

pressed and dried. It forms a red powder which dyes wool red tints. veryfast to washing, fulling. sulphur and light.

2. The diazo-solut-ion prepared as described in Example 1 is mixed witha solution, alkaline with sodium carbonate. of 76 parts of sodium1-naphthol-3.8-disulphonate. The dyestufii is salted out cold, pressedand dried. It forms a blue red powder which dyes wool red tints fast tofulling and washing and of remarkable fastness to light.

. 3. The diazo-solution made according to Example 1 is mixed with asolution, made alkaline with sodium carbonate, of 78 parts of 1-acetylamino-8 naphthol 3.6 disu-lphonic acid. The dried dyestufl forms aviolet powder which dyes wool violet tints of good tastness to washing,fulling and sulphur.

4. The diazo-solution obtained in the usual manner from 29.5 parts of4.4-diamino-3.3- dimethyl-2.2-dichlorodiphenylmethane is mixed with asolution alkaline with sodium carbonate of 1(2-chlorophenyl-5-sulphonicacid) -3-methyl-5-pyrazolone and the dyestufl is finished in the usualmanner. When dried it is a yellow powder which dyes wool greenish-yellowtints of good fastness to washing. and fulling.

Similar tints are yielded by the dyestufi' which may be made inaccordance with this example by starting from 4.4-diamino-3.3.6.6'-tetrachlorodiphenylmethane.

5. The diazo-solution prepared as described in Example 1 is mixed with asolution alkaline with sodium carbonate of 48.8 parts of2-naphthylamino-6-sulphonic acid.

When combination is complete the dyestuff is salt-ed out. pressed anddried. There is obtamed a yellow red powder which dyes wool orange tintsfast to phur.

6. The diazo-solution made as described in Example 1 is mixed with asolution containing 30 parts of beta-naphthol and 24 parts of causticsoda solution of 40 Baum specific gravity, with addition of the usualproportion of sodium carbonate. The dyestufi is finished in the knownmanner. There is obtained a red brown pigment of very good properties offastness.

The following table gives a summary of dyestuffs which may be made inaccordance with the invention. It is not exhaustive and could, indeed,be very much extended.

washing, fulling and sul- (a) Wool dyestufis Solution in con- Oolor ofthe Azo-component Dyeing on wool centrated sulpowder phuric acid 4.4l;'diamin0-3.3'-dichlorodiphenylme- 2-naphtliyl-amino-6-sulphonicacid. Yellow-red. Orange. Violet.

t ane- Do. Sodium 2-naphtliol-6-sulphonato. Red. Reddish orange. Red.Do. Z-naphthol-B-sulphonic acid. Yellow-red. Yellow-red. Red-brown. Do.1-naphthol-5-sulphouic acid. Brown. Red. Violet. Do.1-naphthol-4.8-disulphonic acid. Bordeaux. Red. Red. Do.l-naphthol-3.6-disulphonic acid. Bordeaux. Red. Bordeaux. Do.l-uaphthol-3.S-disulphonic acid. Bordeaux. Red. Red. Do.2-naphthol-3.6-disulphonlc acid. Bordeaux. Red. 1 Red. Do. Sodium2-naphthol-4-sulphonatc. Bordeaux. Blue-red. Bordeaux. Do. Sodium1-naphthol-4-sulphonate. Bordeaux. Blue-red. 3 Red. Do.Ethyl-chromotropic acid. Red-brown. Blue-red. l Blue. Do, Chromotropicacid Bordeaux. Bordeaux. Blue. Do. l-acetylamino-S-naphthol 3 6 dis ulViolet. Violet. Bordeaux.

phonic acid. Do. 1-amino-8-naphthol-4-sulphonic acid. Brown. Violet.Blue. Do. 1 2-chloro'5 -sulphophenyl-3-methyl-5- Yellow.Greenish-yellow. l Yellow. pyrazolone. Do. l-phenyl-3-rnethyl-5-p y r az 01 o n e 5111- Yellow-brown. Yellow. Yellow.

phonic acid. 4 4 diamino-3.3'-6.6-tetrachlorodiphe- 1.2-hloro-5'-sulphophenyl-3-m e t h 3! 1- Yellow. Greenlsh-yellow. Yellow.

nylmethane. 5-pyrazolone. 4 4' -diamino-3.3-dimethyl-2.2-dichld1.2-chloro-5-sulphophenyl-3-methyl-5- Yellow. Greenish-yellow. Yellow.

rodiphenylmethane. pyrazolone.

i Gives violet chrome lake.

The structure of the third dyestufi in the above table, formed bycoupling 3.3 -dichlorodiphenylmethane with cthyl-chromotropic acid, maybe represented by the following formula 02H) on c1 o1 on 002115 someNaOaS SO;Na

NaOaS The structure of the seventh dyestuff formed by coupling3.3-dichlorodiphenylmethanc ,With1.2-chloro-5-sulpho-phenyl-3-methyl-5-pyrazolone may be represented bythe following formula:

C1 01 H H CHzfi(:JN=N CH =N-d cn3 N 0 0E N I? N (,1 0 01 Cable NaOi S(b) Cotton dyestuffs Azo-eomponent Color on cotton4.4-diamlno-3.3-dichlor0dlphenylmetliane. I1-amino-8-naphthol-3.G-disulphonic acid. l Violet.

Do. 2-amino-5-naphthol-7-sulphonic acid 2 p h c n y l a In in o 5Corinth. naphthol-7-sulphonic acid. Do.[1-amino-8-naphthol-3.o-disulphonic acid (acid) 4'ni tra n i-Green-blue.

- line] (alkali). Do. [li mgnzmiriigaphthol-ly.fi-disulpllonic acid(alkali) 4-nitrani' Green-blue.

DB BCl Do. l-amino-8-nap thol-3.6-disulphonic acid (acid) an d2-hydroxy- Violet.

naphthalene (alkali). Do. Z-amin0-5-naphth0l-7-sulph0nic acid. Bordeaux.

In the'above table the arrows indicate diazotization and coupling andpoint from the diazo component toward the coupling component.

The structure of the fourth dyestuif given in Table I) may berepresentedby the following formula:

(0) Lake dyeelufa I Am-eo mponent Color of the lake 4.4-diamino-3.3-dichlorodiphenylmethane. 2-hy iroxynaphthalenm Red-brown.Do. z-hydroxynaphthalene-a-eerboxyhe acid. Red-brown. Do.z-hgdroxynaphthalene-a-carboxyllc acid-anilide. Bordeaux. Do. l-penyl-a-methyl-fr-pyrazolone. Yellow.

As will be apparent from Table 6' the disome cases be coupled withdiazocompounds. sa-zo dyestuffs obtained aocordin to the ex- What weclaim is,- amples can either, in so far as my contain 1. Thehereindescribed new azo dyes havdiazotizable aminogroups, diazotized anding a very good fastness to fulling and light 5 combined with furtherazo components, or in and corresponding to the .general formula: 10

Halogen Halogen v v econ 7 mo 2. The hereindesoribed new azo dye havinga very good fastness to falling and light and corr esponding to thegeneralformula:

on mo 3.- The hereindesoribed new azo dyes. hating a very good fustnessto fulling and light and corresponding to the general formula.

mm mo I 15- wherein at least one symmetricel'X- Y pair In testimonywhereof we aflix our signarepresent-halogen, and one othersymmetritures. t

cal X Y pair represent on 'of thegroup v hydrogen, alkyl, and halo en,and the other RUDOLPH KREGH. Xs and Ys represent hy' rogen. v ERICJHKEINEB.

